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RETRACTED ARTICLE

Rhodium-catalyzed arylative and alkenylative cyclization of 1,5-enynes induced by geminal carbometalation of alkynes.
J Am Chem Soc. 2006 Dec 13; 128(49):15598-9.JA

Abstract

A rhodium(I)-catalyzed addition-cyclization of 1,5-enynes with aryl- and alkenylboronic acids has been developed. The reaction allows for efficient C-C coupling of multiple reactive components while accomplishing a net R,H-addition in a single step under mild conditions. In the presence of [Rh(OH)(COD)]2 catalyst and triethylamine base in methanol solvent, a range of 1,5-enynes undergo an intermolecular addition with a wide variety of aryl- and alkenylboronic acids and concomitant endo-selective cyclization to yield 1-aryl and alkenyl-substituted cyclopentene derivatives as the products. Deuterium labeling studies suggest that the reaction involves formation of a rhodium vinylidene complex with the terminal alkyne of the enyne substrate. The subsequent migration of the aryl or alkenyl group from the rhodium center to the alpha-carbon of the vinylidene ligand gives a vinyl rhodium complex, a formal 1,1-carbometalation process of the alkyne. This vinyl rhodium then adds to the pendent alkene, and the protodemetalation of the resulting rhodium enolate affords the product.

Authors+Show Affiliations

Chen Y
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
Lee C
No affiliation info available

MeSH

AlkadienesAlkynesCatalysisCyclizationHydrocarbons, AromaticMolecular StructureOrganometallic CompoundsRhodiumStereoisomerism

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.
Retracted Publication

Language

eng

PubMed ID

17147363

Citation

Chen, Yiyun, and Chulbom Lee. "Rhodium-catalyzed Arylative and Alkenylative Cyclization of 1,5-enynes Induced By Geminal Carbometalation of Alkynes." Journal of the American Chemical Society, vol. 128, no. 49, 2006, pp. 15598-9.
Chen Y, Lee C. Rhodium-catalyzed arylative and alkenylative cyclization of 1,5-enynes induced by geminal carbometalation of alkynes. J Am Chem Soc. 2006;128(49):15598-9.
Chen, Y., & Lee, C. (2006). Rhodium-catalyzed arylative and alkenylative cyclization of 1,5-enynes induced by geminal carbometalation of alkynes. Journal of the American Chemical Society, 128(49), 15598-9.
Chen Y, Lee C. Rhodium-catalyzed Arylative and Alkenylative Cyclization of 1,5-enynes Induced By Geminal Carbometalation of Alkynes. J Am Chem Soc. 2006 Dec 13;128(49):15598-9. PubMed PMID: 17147363.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Rhodium-catalyzed arylative and alkenylative cyclization of 1,5-enynes induced by geminal carbometalation of alkynes. AU - Chen,Yiyun, AU - Lee,Chulbom, PY - 2006/12/7/pubmed PY - 2007/3/3/medline PY - 2006/12/7/entrez SP - 15598 EP - 9 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 128 IS - 49 N2 - A rhodium(I)-catalyzed addition-cyclization of 1,5-enynes with aryl- and alkenylboronic acids has been developed. The reaction allows for efficient C-C coupling of multiple reactive components while accomplishing a net R,H-addition in a single step under mild conditions. In the presence of [Rh(OH)(COD)]2 catalyst and triethylamine base in methanol solvent, a range of 1,5-enynes undergo an intermolecular addition with a wide variety of aryl- and alkenylboronic acids and concomitant endo-selective cyclization to yield 1-aryl and alkenyl-substituted cyclopentene derivatives as the products. Deuterium labeling studies suggest that the reaction involves formation of a rhodium vinylidene complex with the terminal alkyne of the enyne substrate. The subsequent migration of the aryl or alkenyl group from the rhodium center to the alpha-carbon of the vinylidene ligand gives a vinyl rhodium complex, a formal 1,1-carbometalation process of the alkyne. This vinyl rhodium then adds to the pendent alkene, and the protodemetalation of the resulting rhodium enolate affords the product. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/17147363/Rhodium_catalyzed_arylative_and_alkenylative_cyclization_of_15_enynes_induced_by_geminal_carbometalation_of_alkynes_ L2 - https://doi.org/10.1021/ja067125+ DB - PRIME DP - Unbound Medicine ER -